Aqueous emulsion-suspension textile treating compositions and processes of treating textiles with same



States AQUEOUS EMULSlfiN-SUSPENSION TEXTILE TREATING CfiMPQSETllONS ANDPROCESSES (BF TREATWG TEXTILES WITH SAME No Drawing. ApplicationNovember 9, 1954, Serial No. 467,902

9 Claims. (Cl. 2629.4}

(Granted under Title 35, U. S. Code (1952), see. 266} A non'exclusive,irrevocable, royalty-free licensein the invention herein described, forall governmental purposes, throughout the world, with the power to grantsublicenses for such purposes, is hereby granted to the Government ofthe United States of Arnerica.

This invention relates to improving the properties of cellulosic textilematerials by impregnating them with resin. More particularly, theinvention provides cellulosic textile materials containing a resinousimpregnant which imparts flame resistance in addition to other desirabletextile properties or which imparts an unusually great flame resistancefor the amount resinous impregnant.

Prior work has resulted in the development of a variety of polymerscapable of being produced by condensation and/ or esterificationreactions involvingtetrakis(hydroxymethyDpho-sphonium chloride, whichhas the formula (HOCH2)4PC1, and is abbreviated THPC, and/ ortris(hydroxymethyl)phosphine oxide, which has the formula (HOCH2)3PO,and is abbreviated THPO. The methylolphosphorus, PCHZOH groups, of eachof these compounds are capable of either: (1) condensing with a compoundwhich is capable of condensing with formaldehyde, or (2) beingesterified by an esterifying agent which is capable of esterifyingmethanol. Compounds of the group, THPC, THPO, and derivatives of eitherof them which contain a plurality of methylol-phosphorus groups of thepresent compounds, are hereinafter referred to by the term phosphoruscompounds.

The polymers capable of being produced by condensation and/oresterification reactions of the phosphorus compounds can be produced inthe form of cross-linked polymers or thermosetting resins. Hereinafter,these polymers are referred to by the term methylol-phosphorus polymersor resins. The compounds capable of either condensing with formaldehydeor esterifying methanol are hereinafter referred to by the termmethylol-reactive compounds.

The methylol-phosphorus polymers are characterized by recurringstructural units containing phosphorus atoms in radicals of the group(-CH2)4PC1 and (CH2)3PO. Methylol-phosphorus alkyds are produced byreacting at least one of the phosphorus compounds with at least onepolycarboxylic acid esterifying agent. Phenolic methylol-phosphoruspolymers are produced by reacting at least one of the phosphoruscompounds with at least one phenolic compound.

Certain nitrogen containing methylol-phosphorus polymers, which arehereinafter referred to as nitrilo methylol-phosphorus polymers orresins, are particularly useful as textiie flammability retardants.These resins are adapted to being partly or completely formed within thetextile by impregnating the textile with an aqueous solution ordispersion of their resin forming reactants, and causing the reactantsto react in situ until an insolubilized resin is produced. Thenitrilo-methylol-phosphorus polyatent mers are capable of, beingproduced by condensing at.

ice

least one of the phosphorus compounds, with the elimination of water,with at least one organic nitrogen compound having a molecular Weight ofnot more than about 400 and containing at least one trivalent nitrogenatom and at least two members of the group H and CHzOH attached totrivalent nitrogen atoms. This class of organic nitrogen compounds ishereinafter referred to by the term nitrogen compounds. Methods ofproducing the nitrilo-methylol-phosphorus polymers and employing them toreduce the flammability of textiles are more completely described incopending patent applications, Serial No. 378,437 filed September 3,1953; Serial No. 393,021, now Patent No. 2,772,188; and Serial No.393,023 filed November 18, 1953, now Patent No. 2,795,569.

in a process of impregnating a textile material with a thermosettingresin, the resin is usually prepared in a further polymerizable form andincorporated into a textile treating agent comprising a liquidsolutionor emulsion. The use of aqueous solutions or emulsions is particularlyadvantageous because of the reduced fire hazard. The textile materialsare impregnated with such textile treating agents, dried, and thensubjected to conditions which insolubilize the polymers in situ.

Such a treatment produces textile materials the fibers of which areeither coated with or contain the insolubilized thermosetting resin.When the fibers of textile materials are so treated withnitrilo-methylol-phosphorus polymers, the textiles are renderedmaterially less flammable; and when the fibers are so treated withaminoplast polymer the materials are rendered materially more wrinkleresistant.

However, it has been found that while such an impregnation materiallyimproves the properties of the heavier fabrics, it is often difficult toobtain the desired degree of flame resistance in the lighter weightfabrics without adversely altering other properties of the fabrics. Forexample, it is often difhcult to adequately fiameproof fabrics of lessthan about 7 ounces per yard, or to impart to' any fabric an appreciableincrease in both wrinkleresistance and flame resistance, without causingan undesirable increase in the stiffness of the fabric.

In addition, further polymerizable polymers contained in liquid textiletreating agents tend to polymerize on standing, and in general, it isnecessary to prepare the further polymerizable resin and incorporate itin the liquid textile treating agent just shortly before the textiletreating agent is to be applied to a textile. This is somewhatdisadvantageous to numerous textile treating concerns which are notequipped to carry out the chemical process involved in the production ofthe further polymerizable resin.

An object of the present invention is to provide an aqueous textiletreating composition which will deposit a laundering and dry cleaningresistant resinous substance in a textile impregnated with thecomposition so as to impart an unusually high degree of flame-resistanceto the textile without materially increasing its stiffness. Anotherobject is to provide an aqueous textile treating composition by whichboth the Wrinkle resistance and the frame resistance of a textile can bematerially enhanced with a single treatment. A further object is toprovide an aqueous textile treating composition which can be prepared bysimply agitating a mixture of stable compounds without conducting anycontrolled partial polymerization reaction. i

In general, in accordance with this invention, aqueousemulsion-suspension textile treating compositions are produced byagitating, to form an aqueous emulsion, a mixture of (a) Water soluble,cotton fiber penetrating, resin forming reactants of at least one resinof the group, aminoplast and nitrilo-methylol-phosphorus resins, (b) arelatively inert. water immiscible organic liquid, (c) an emulsifyingagent;'(d) eno h water to form a stable oil-in-water emulsion; Tn thisoil-in-water emulsion, an amount of powdered insolubilizedphosphorus-containing thermo setting resin is dispersed, providing-inthe result- Ting ernulsiomsuspension, from about to 80. parts ofinsolubilized jre'sin per 100 parts of resin forming reactants in whichis present jat'ileast about 0.1 parts of phosphorus per'oart-of nitrogenV 1 i t When textilemateria'ls containingcellulosic fibers areimpregnated with such aqueous compositions, andrthe 'resingformingreactants are converted to resins in situ, the sogtreated textilematerials become impregnated with an insolubilizedthennosetting'resin'in the form of a continuous resin; phase whichextendsflinto thecellulosic fibers and'which surrounds disperseddiscreet solid particles of an insolubilized resinr These particles 'arepresent in"proportions which, in coniunction with the continuous phase,imnart'a imate'rially improved flame resistance to .the textile. s 1 iWhere a textile materialcontaining cellulosic fibers is impregnated withan aqueousemulsion-suspension containing the resin forming reactantsofaan aminoplast resin so that the resinpick-unof the textile 'is fromabout 7 to 35 %of total resinous materials, where the proportions of.the resinous materials are such that from about4 to 20% of the resinousmaterial pick-up 'consists'ofthe aminoplastresin forming reactants, andwhere theresin forming reactants are converted to a resin in situ, boththe wrinkle resistance and the flame resistance of the sotreated textilematerial are materially enhanced. The wrinkle resistance and thestiffness of the so-treated textile'is'substantially the same as that ofa textile to which'only the aminoolast resin has been applied in theusual way: but the textile material treated with the aqueousemulsion-suspension composition exhibits a materially greaterflameresistance When a textile material containing cellulosic fibers isimpregnated with an aqueous emulsion-suspension containing nitrilomethylol-phosphorus resin forming reactants and the resin formingreactants'are converted to a resin in situ, the so-treated textilematerial is materially .less stiff than one to which the same amountofnitrilomethylol-phosphorusresin is applied in the usual way and enouh. additional phosphorus containing resin is added inthe usual way toimpart thesamedegree of flame resistance. V t

'Substantially'any of the natural or synthetic organic textile materialsin the formof fibers, yarns, threads, on

fabrics can be treated in accordance with the present invention.Suitable materials include cotton, flax, ramie, Wool, silk, regeneratedcellulose such as the viscose rayons, mercerized cellulosic textilematerials and. the like. The process is particularly adapted to thetreatment of threads or fabrics containing cotton and regenerated cel-Iulosefibers. The water soluble, cotton fiber penetrating resin formingreactant can be: (1) polymeric reactants such as, a

further. 'polymerizable. aminoplast or nitrilo-methylolphosphoruspolymer which is both water soluble and capable of penertating into acotton fiber; or (2) monomeric reactants, such as a substantiallyunreacted mixture of at leaston'e water soluble organic nitrogencompound with: (a) at least'one aldehyde capable of yielding aminoplastresins, or (b) at least one water. soluble phosphorus compound. i a 1 VIllustrative examples of suitable water soluble, cotton fiberpenetrating further polymerizable aminoplast polymer s'includetthecondensation polymers of amino, imine, 'amido, or imido compounds'withaldehydes such as those described in Modern Plastics 17, 433, 1939, orChemistry ofsynthetic resins .[by C. Ellis, published by ReinholdPublishing Corp, chapter 26 (1935)], which vare both water solu'ble andcotton fiber penetrating, i. e.

which have a molecular weight low enough to allow them to penetrate intoa cotton fiber. In general, the further polymerizable aminoplast ornitrilo-methylol-phosphorus polymers having a molecular Weight lowenough to penetrate into a cotton fiber are completely water solublepolymers. Whether a given further polymerizable aminoplast or'nitrilo-methylolphosphorus polymer has a molecular weight low enough topenetrate into a cotton fiber can readily be ascertained byimpregnating. cotton fibers with the polymer andobr serving stainedsections of the impregnated fibers under a microscope (by the method].T. Marsh).

Suitable nitrilo-methylol-phosphorus polymers comprise condensationpolymers of at least one phosphorus compound with at least one'nitrogencompound, such as the polymers Which are more fully-described incopending applications, Serial Nos. 378,437 and 393,023, which are watersoluble and cotton fiber penetrating.

Suitable mixtures of a water soluble nitrogen compound with a watersoluble aldehyde include mixtures of at least one such nitrogen compoundwith at least one such aldehyde; Illustrative examples of such aldehydesinclude: formaldehyde, propiolaldehyde, butyraldehyde, and the likewater soluble aldehydes; In general, any Water soluble'aldehyde capableof reacting to form an aminoplast can'be used. However, the watersoluble aliphatic aldehydes containing 1 or 2 carbon atoms arepreferred. s p 7 Suitable mixtures of a water soluble nitrogen compoundwith a water soluble phosphorus compound include mixtures in which thephosphorus compound is THPC, THPO, or a water soluble reaction productof either of them with .a methylohreactive compound, (i.'e.

a compound capable of condensing with formaldehyde or esterifying methylalcohol) which; reaction product is water'soluble and retains aplurality of the PCHzOH groups of the PCHzOH groups of the parentcompound.

Illustrative examples of compounds capable of condensing 'withformaldehyde include: the nitrogen compounds, such as melamine, urea,dicyandiamide, ethylen imine, trimethylenepentamine, stearylamine andthe like; and phenoliccompounds such as phenol, 'resorcinohand the like.

Illustrative examples of compounds capable of esterifying methyl alcoholinclude the mono and polycarboxylic acid esterifying agents such asacetic anhydride, butyryl chloride, stearic acid, phthalic acid,chlorendic acid, succinyl dichloride and the like.

The relatively inert water immiscible organic liquids which can be usedcomprise waterimmiscible liquids which are inert toward the textilematerials, the thermosetting resins and their resin forming reactants.The water immiscible organic solvents which boil at from about to 210 C.are particularly suitable. Illustrative examples of such organicsolvents include aliphatic hydrocarbons such as octane, nonane,cycloparaflins such as 1,2-dimethylcyclohexane and n-propylcyclohexane,the hydrocarbon mixture available under the trade name of Varsol, andthe like aliphatic. hydrocarbons. .The aliphatic hydrocarbons boiling atfrom about 177 to 204? C., such as the above-mentioned Varsol, arepreferred.

Substantially any of the conventional emulsifying agents, or mixturesthereof,.can be used in the present process. Illustrative examples ofsuitable emulsifying agents include the tertitary amine salts of longchain fatty acids such as triethanolamine stearates, oleates, and thelike; the sulfated long chain alcohols; dioctyl sodium succinate,carboxymethyl cellulose, the polyvinyl alcohols, and the like.

The proportions of the oil and Water phases of the oilin-water emulsionscan be varied Widely as long as the resulting emulsion is stable for atleast an hour. Both the proportion and number of emulsifying agents canbe varied widely; but the use of less than about 5 parts of emulsifyingagent per partcf emulsion ispreferred.

In preparing the emulsions, an organic liquid solution and an aqueousliquid solution are preferably prepared separately; then mixed togetherwith vigorous agitation. A colloid mill is a particularly suitableagitating device. The emulsifying agent can be dissolved in either theorganic or the aqueous solution, but is preferably dissolved in theorganic solution, or formed in situ between the phases of the emulsion,e. g., by dissolving a long chain fatty acid in the organic solution anddissolving an amine in the aqueous solution so that they react to forman amine salt emulsifying agent when the solutions are mixed.

The use of amine salt emulsifying agent in which the amine is a watersoluble tertiary amine such as triethanolamine, ethyl diethanolamine andthe like, is preferred. The presence of such a water soluble tertiaryamine in an aqueous solution containing a further polymerizablenitrilo-methylol-phosphorus polymer tends to inhibit the formation ofwater insoluble polymers prior to the heating of the furtherpolymerizable polymer to a temperature materially above normal roomtemperature. In a preferred embodiment of the invention an amine saltemulsifying agent is formed in situ in the emulsion by dissolving theamine in the aqueous phase and dissolving a high molecular weight acidsuch as a long chain fatty acid, a rosin acid, or the like, in theorganic phase.

The powdered insolubilized phosphorus-containing brittle resin can beany relatively unreactive brittle resin which is insoluble in aqueous ororganic solvents and is ground to a powder. Such resins preferablycontain at least about 5% phosphorus or 1% phosphorus if the resincontains at least bromine.

Illustrative examples of phosphorus-containing resins which can beemployed as the powdered insolubilized resin include: (1) nitrogencontaining insolubilized methylol-phosphorus resins capable of beingproduced by reacting at least one phosphorus compound with at least onenitrogen compound containing at least two members of the group H andCHzOH attached to trivalent nitrogen atoms until the reaction product isan insoluble brittle solid, such as the insolubilizednitrilo-methylol-phosphorus resins which are more completely describedin copending applications, Serial Nos. 378,437, 393,021 and 393,023; theresins produced by an analogous reaction of a phosphorus compound withan inorganic derivative of ammonia containing a plurality of hydrogenatoms attached to trivalent nitrogen atoms such as ammonia, hydrazine,hydroxylamine, etc., or with an aromatic amino compound containing aplurality of members of the group H and CHzOl-I attached to trivalentnitrogen atoms, such as aniline, the methylolated anilines,diphenylenediamine, etc. and the like nitrogen containing insolubilizedphosphorus resins; (2) solid, insoluble phosphonitrilic ester adductsproduced by substantially completely reacting at least one terminallyunsaturated, polymerizable, alkenyl alcohol ester of a phosphonitrilichalide with at least one polyhalohydrocarbon containing at least twohalogen atoms of the group bromine and chlorine attached to the samecarbon atom, in the presence of a free radical reaction initiator, toproduce a halomethylated alkenyl phosphonitrilic polyester-adductcontaining phosphorus, nitrogen, and halogen, which phosphonitrilicester adducts and processes for their production are more fullydescribed in copending application Serial No. 467,900, filed of evendate; (3) solid insoluble bromine containing methylolphorphorus resinsproduced by substantially completely reacting at least one phosphoruscompound with at least one bromine containing compound of the grouppolyfunctional nitrogen compounds and polyfunctional methylol-reactingcompounds, which bromine containing nitrilo-methylol-phosphorus are morefully described in copending application Serial No. 467,898, filed ofeven date; (4) the phenolic methyloi-phosphorus resins capable of beingproduced by reacting at least one phosphorus compound with at least onephenolic compound capable of condensing with formaldehyde, such as thebromohydroquinones, the methylolated phenols, the bromophenols,naphthols, etc., until an insolubilized resin is produced, examples ofwhich include the insolubilized phenolic methylol-phosphorus resinswhich are more completely described in copending application Serial No.348,137 filed April l0, 1953, now abandoned; (5) alkyl typemethlyol-phosphorus resins capable of being produced by reacting atleast one phosphorus compound with at least one polyfunctional acidesterifying agent until the reaction product is an insolubilized brittlesolid, such as the insolubilized methylol-phosphorus alkyds produced byreacting a phorphorus compound with a polyfunctional carboxylic acidesterifying agent, such as chlorendic acid, which is more completelydescribed in copending application Serial No. 393,020 filed November 18,1953; (6) solid, insoluble polymeric addition products of polyhalohydrocarbons and polymerizable unsaturated neutral esters of phosphoricacid such as those more fully described in copending application SerialNo. 403,943, filed lanuary 13, 1954 now U. S. Patent 2,778,747, and U.S. Patents Nos. 2,686,768 and 2,686,769; (7) solid, insoluble brominatedpolymers of polymerizable unsaturated esters of phosphoric acid; and (8)solid, insoluble polymeric reaction products of phosphorus oxychlorideand ammonia.

The insolubilized phosphors containing brittle resins can be powdered bycomminuting them in any apparatus suitable for comminuting polymers. Thepolymers are preferably ground to a particle size at least small enoughto pass through a standard screen of about 300 meshes per inch.

The amount of insolubilized powdered phosphorus containing resin whichis suspended in the oil-inwater emulsions can be varied widely. Theoil-in-water emulsions which are stable for at least an hour generallyremain stable when up to about 0.2 parts of powdered insolubilized resinper part of emulsion is suspended in them. The suspension of as littleas 50 parts of powdered insolubilized phosphorus containing resin perparts of emulsion produces emulsion suspensions which impart anappreciable increase in flame resistance to textiles impregnated withthe emulsion suspension.

Where it is desired to concurrently impart both flame resistance andwrinkle resistance to a cellulosic material, resin forming reactants ofeither the nitrilo-methylolphosphorus or the aminoplast resins can beused; but the use of the aminoplast resin forming reactants ispreferred. In accomplishing such a result it is preferable to employless than about 20 parts of the resin forming reactants per 100 parts ofan aqueous emulsion suspension containing not more than about 15 partsof powdered insolubilized thermosetting resin. Textiles are preferablyimpregnated with such emulsion suspension so that there is a resinadd-on of the resin forming reactants of not more than about 20%.

The cellulosic textile materials can be impregnated by substantially anyof the usual processes of impregnating textiles with aqueous emulsionsusing the usual apparatus and the usual wet pick-ups. In general, wherea high resin add-on (percent increase in the weight of the dry textilematerial due to the resin incorporated in the textile material) isdesired, it is preferable to employ a plurality of impregnating steps.The impregnated textiles are preferably mechanically freed of excessliquid and dried at from about 70 to C. for a time sufficient to removethe bull; of the volatile materials.

After the textile materials have been impregnated with the emulsionsuspensions the resin forming reactants are converted, in situ, toresins. The conversion, or insolubilization, can be accomplished bysubstantially any of the procedures usually used in the insolubilizationof aminoplast or nitrilo-methylol-phosphorus polymers. Thermalinsolubilization, by heating the impregnated textile materials to atemperature of from about 110 to C. for from about 2 to 20 minutes withthe longertime t are particularlyisuitable for 6- tog9lo z} .twills orsateen;

being used in conjl lncti on with the lower temperature, is preferredInsolubilization temperatures and times: of from about- 140 to 1:55 :C.fonfrom about 4 to 6minutes .taining about 8.4 parts of. resin formingreactants and about. 16 parts of powdered insolubilized resin per 100partsof, emulsion suspension. i The resulting emulsionsuspensionwa's'stable for .at least 2 hours.

1 Fed. s en-ooo-r-loib.

The following examples flirther. illustratel details of e h i fl f L M1;"; l AM 3 7 V i": A I T1 I V The efiects-of'a'pplyinganemulsion-suspension compared 'Emn'ls'ified moizomeridnitrilq methylolphosphbi ns1 resin Twill! Q-W f RP J g.a w tinmms phase resin f t f fl viv i f h il i i ti ?llii itii i i ki IA ad u s q f u us was prepared ythe H 4 tt flt ln an;tent rg dl e ds r di E m l 1 using as 7.6. P t A eu i l i fi wa f rm d byia'g'ifafing a i of a Water solublemethylolmelamine, 6.4 parts of urea, ture of (a)nitrilo-methylol-phosphorusiresinlforming re @924 Pa I PQ a d, is 12 P0f Varsol, and actants consisting of 9 parts of. a .water'solublemethylolysm -j pi 'fi fil'g f Suspelldmg P the melamine, 7 partsofure'aand15 parts of .THPC, (b) an msQlublhlfid resmmfhe oll'lnwater lf organic solvent consisting'of 12 parts of Varsol, and an All q o501M101! Was P 'FP y, S g, emulsifying agent consisting of 2 parts ofstearic acid and- Parts of a Water y a e, Parts 9 2;? 2 parts of an oilsoluble long chain alcohol sulfonate, with Parts of H and Parts Otl'lefllanblamlile and 10.6 about parts of Water until the mixturebecame an oil- Parts of I- 7 in-water emulsion which Was stable for atleast an hour. 20 am Q I Q Q Cloth, 211 Square Print IQ In the formationof the emulsion, the resin forming rehavmg about f 'p Y 1 -i actantswere dissolved along with 3 parts of triethauol- 1 twllllwel'e Pfi Wlththe above aqueous 9 3 aminein the water, and the solution so producedwas Wet p -P 0f 3b011t 109 and 76%, fespectlvelys a olution of theemulsifying agents in the (lIle d'fOI about minutes at C. and heated forabout organic Solvent 7 V 5 mlnutes at C. to thermally insolubilize thefurther An insolubilized solid phosphorus containing thermopolymefllablem- 5 setting resin was prepared by dissolving 180 parts of 7 VAcompauson Pfihe P P 'F 0f the treated hs THPC and 69 parts of a watersoluble methylolmelamine Summaflzed 1n l followmgg l The s pl s in about200 parts of water, heating the solution at about w were. treated w tsolutlonrare gn d s 110 c. for about one hour, spreading the resultingvis- .30 pn and 1- and the samples cous liquid into a layer about 0.30inch thick and heating f w re treated fh emUISiOIISUSPeBSiOH are it forabout l hour at about C. The resulting solid slgllatfid' as P andlmulsion.

Stifi'nesstimlb.) ms. Peon Resin Phos- Strip phorus phorus Sample,add-0n, phorus, flame after 10 after 3 hr..,

percent percent .test, launderboil, per- WV-arp Filling deg. ings,percent 'cent,

' Printu ntr eated 0.0 2.s 10- 2.2 10- None Twilluntreated. 0.0 32.4 10-12. 4 10- None 4 Prints0lution. 10.3 5. 2x10- 6.2X10-4 1.40 135 1.401.47 Twjn ]ution L4 12.2 10- 1.04 105 1.01 0. 96 Printemulsion 26.7 4.s10 3 6 10 1.88 1.67 1.96 Twill-emulsion. V 15.8 33.5x10- 16.8X10-4 1. 34140 1.14 1 .24

2 Fabric was boiled 3 hours in a solution containing 1.0% soap chips and0.2% sodium carbonate.

emulsion-dispersion containing 34 parts 'of resin forming reactants,about 11 parts of powdered insolubilized resin per 100 parts of emulsionsuspension;

' EXAMPLE 2 j Emnlsified monomeric aminoplasi resin forming reactantswith st lspended insolubilized nz'trilo-methylol-phosphorus resin Anaqueous emulsion was formed by agitating a mixture of (a) an aminoplastresin forming reactant consisting of 9 parts of a water solublemethylolmelamine, (b) an organic solvent consisting of 15 parts ofVarsol, and (c) an emulsifying agent consisting of '2 parts of a longchain water soluble alcohol sulfonate and 2 parts of stearic acid withabout 60 parts of water until the mixture became a stable oil-in-wateremulsion. In the formation of the emulsion, the resin forming reactants,and the alcohol sulfonate were dissolved in water along with 2.4 'partsof triethanolamine and the resulting solution was'mixed with a solutionof the stearic acid in the oil solvent;

aqueous emulsion to produce an emulsion-dispcrsioncon- The flameresistance of the treated cloths'were-compared by the strip flame test.-In this method a /2 inch strip of the cloth is held at one end so thatit extends to.- ward some degrees between Oand, relative to a verticalazimuth. The far ends of the so held strips'are ignited by contactingthem with an open flame and flame is re moved as the cloth is ignited;Untreated cotton cloth will propagate a flame straight down and willburn at .0 (i. 6., when heldto extend vertically and ignited at. the topThe degrees in the abovetable indicate the degrees to Ward which thevarious cloths were pointed when they would not'continue to supportcombustion after being ignited at the end. Those which would notcontinue to burn when pointed toward degrees between 135 and 180 whereconsidered to exhibit relatively low 'combustibility.

7 EXAMPLE 4 Emulsifiea' monomeric nitrz'lo-methylol-phosphorus resinformingreactants with suspended powered isolubilized methylol-phosphorusresin 'of a water, soluble methylolmelamine and 6.0 parts of urea, as(b) 12 partsof Varsol, as (c) 2 parts of stearic acid and 2 parts oflong chain alcohol sulfate (Dupanol 'G), and about 56 parts of water. 7An insolubilized ammonia methylol-phosphorus resin was prepared bydissolving 19 parts of fII-IPC- in 19 parts of water and mixing.thesolutionwith 10 parts of concentrated ammonium hydroxide. Withinabout 3 minutes a substantially colorless solid resin was precipitated.The resin was water Washed until washings were neutral and then dried.The dried resin had the form of a fine powder the particles of whichwould pass a standard 300 mesh screen after grinding in a motor.

About parts or" the powder was suspended in the oilin-water emulsion toproduce an emulsion-dispersion containing about 23 parts of resinforming reactants, and about 9 parts of powdered insolubilized resin per100 parts of emulsion suspension.

An 80 by 80 cotton print cloth was padded with the emulsion-suspensionto a Wet pick-up of about 90%, dried at about 90 C. and heated for about4 minutes at 150 C. After washing to remove any adhering water solublesalts and air drying, the fabric was found to contain about resin. Thefabric had a good hand and a strip of the fabric would not continue tosupport a time at 150 angle.

EXAMPLE 5 Emztlsified monomeric nitrilo-methylol-phosphoru-s resinforming reactants with suspending powdered insoiubilizeti phenolicmethylol-phosphorus resin An aqueous emulsion was formed by theprocedure described in Example 1.

An insolubilized solid phenolic methylol-phosphorus resin was preparedby: dissolving a mixture of 7.6 parts ortho-bromophenol, 8 parts ofTHPC, and 1 part of triethanolamine in 20 parts of water. The solutionwas heated to boiling and maintained at this temperature for about 12minutes until a jell formed. The jell was broken up and heated for about40 minutes at a temperature of about 140 C. in a forced draft oven. Theresulting dry resin was ground into particles which would pass astandard 300 mesh screen.

About 7 grams of the powdered insolubilized resin was suspended in theoil-in-water emulsion to produce an emulsion-suspension containing about23 parts of resin forming components and about 10 parts of powderedinsolubilized resin per 100 parts of emulsion suspension.

An 80 by 80 cotton print cloth was padded with the emulsion-suspension,dried at 90 C. and heated for 4 minutes at 150 C. After washing toremove any adhering water soluble salts and redrying, the fabriccontained about 24% resin. The fabric had a good hand and would notcontinue to support a flame at 150 angle.

Example 6 Emulsified monomeric nitrilo-methylol-phosplzorus resinforming reactants with suspended powered insolubilized allylphosphonitrilic polyester-bromoform adduet An emulsion was prepared asdescribed in Example 1 using 12.2 parts of THPC, 7.1 parts of a watersoluble methylolmelamine, 6.5 parts of urea, 3.1 parts oftriethanolamine, 45.6 parts of Water, 1.7 parts of a long chain alcoholsulfate, 3.4 parts of oleic acid and 10.2 parts of Varsol.

10.2 parts of a bromoform adduct of the ester of allyl phosphonitrilicchloride (made by using 0.6 mole of bromoform per mole of diallyl esterof phosphonitrilic chloride according to procedure described incopending application Serial No. 467,900) was suspended in the emulsion.

A sample of 8 oz. twill cotton cloth was padded through the emulsion,dried at 180 F. then cured 6 minutes at 290 F. After washing the fabricin hot tap water containing 21 water softener and drying it, the fabricpassed the 180 angle strip flame test. The resin impregnated fabricexhibited good hand and tear strength properties.

We claim: I

l. A textile treating composition comprising an aqueous emulsionconsisting essentially of an inert water-immiscible organic liquid, anemulsifying agent, enough water to form v 1Q a stable oil-in-wateremulsion, and water-soluble resinforming reactants from the groupconsisting of (a) aminoplast resin forming reactants and (b)phosphorus-containing resin forming reactants comprisingtetrakis(hydroxymethyl) phosphonium chloride and at least one organicnitrogen compound having a molecular weight less than 400, said nitrogencompound having at least one trivalent nitrogen atom and at least tworadicals from the group consisting of H and CH2OH attached to trivalentnitrogen atoms, and dispersed in said aqueous emulsion, a powderedinsoluble phosphorus-containing resin from the group consisting of (1)resins produced by reacting tetrakis(hydroxymethyl) phosphonium chloridewith at least one organic nitrogen compound having at least onetrivalent nitrogen atom and at least two radicals from the groupconsisting of H- and CH2OH attached to trivalent nitrogen atoms, (2)resins produced by reacting etrakis(hydroxymethyl) phosphonium chloridewith an inorganic trivalent nitrogen-containing compound, (3) resinsproduced by reacting tetrakis(hydroxymethyl) phosphonium chloride with aphenolic compound capable of condensing with formaldehyde, and (4)resins produced by reacting a terminally unsaturated polymerizablealkenyl alcohol ester of a phosphonitrilic halide with apolyhalohydrocarbon containing at least two halogen atoms from the groupconsisting of chlorine and bromine attached to the same carbon atom,said insoluble powdered resin being present in an amount to provide inthe resulting emulsion-suspension, from about 0.2 to 2.0 parts ofinsoluble resin per one part of resin monomer, and at least about 0.1part of phosphorus per part of nitrogen.

2. The textile treating composition of claim 1 in which the watersoluble resin forming reactants consist of methylolmelamine, urea, andtetrakis(hydroxymethyl)phosphonium chloride and the dispersed powderedinsoluble resin is an insoluble polymer or" tetrakis(hydroxymethyl)-phosphonium chloride and methylolmelamine.

. 3. The textile treating composition of claim 1 in which thewater-soluble resin forming reactants consist of methylolmelamine andthe dispersed powdered insoluble resin is an insoluble polymer oftetrakis(hydroxymethyl)phosphonium and methylolmelamine.

4. The textile treating composition of claim 1 in which theWater-soluble resin forming reactants consist of methylolmelamine, urea,and tetrakis(hydroxymethyl)phosphonium chloride and the dispersedinsoluble resin is an insoluble polymer oftetrakis(hydroxymethyl)phospho- 'nium chloride and ammonia.

5. The textile treating composition of claim 1 in which thewater-soluble resin forming reactants consist of methylolmelamine, urea,and tetrakis(hydroxymethyDphosphonium chloride and the dispersedinsoluble resin is an insolubie polymer oftetrakis(hydroxymethyl)phosphonium chloride and orthobromophenol.

6. The textile treating composition of claim 1 in which thewater-soluble resin forming reactants consist of methylolmelamine, urea,and tetrakis(hydroxymethyl)phosphonium chloride and the powderedinsoluble resin is an insoluble polymeric addition product of an allylester of phosphonitrilic chloride and bromoform.

7. A process of reducing the flammability of a textile fabric withoutmaterially increasing the stifiness of the fabric which comprisesimpregnating the fabric with an aqueous mixture of water soluble,phosphorus-containing resin forming reactants comprisingtetrakis(hydroxymethyl) phosphonium chloride and at least one organicnitrogen compound having a molecular weight less than 400, said nitrogencompound having at least one trivalent nitrogen atom and at least tworadicals from the group consisting of H-- and CH2OH attached totrivalent nitrogen atoms, said aqueous mixture also having dispersedtherein a powdered insoluble phosphorus-containing resin from the groupconsisting of (1) resins produced by reacting tetrakis(hydroxymethyl)phosphonium chloride 11 with at least one organic nitrogen compoundhavingat least one'trivalent nitrogen atom andat least tworadicals fromthe group consisting of H and -VCH2OH attached to trivalent nitrogenatoms, (2) resins, produced by reacting tetrakis(hydroxyme'thyl)phosphonium chloride with an inorganic trivalent nitrogen-containingcompound, (3) resins produced by reacting tetrakis(hydroxymethyl)phosphonium chloride with a phenolic compound capable of condensingwithformaldehyde, and (4) resins produced by reacting a terminallyunsaturated polymerizable alkenyl alcohol ester of a phosphonitrilichalide with ble resin per one part of water soluble resin formingreactants and at least about 0.1 part of phosphorus per part ofnitrogen, drying the fabric and then converting the resinforming'reactants into an insoluble resin in situ in the fabric. v 1 V rt V 8. A process of, concurrently imparting wrinkle-resistance andflame-resistance to a textile fabric which comprises impregnating thetextile fabric with-an aqueous mixture of water soluble resin formingreactants from the group consisting of (a) aminoplast resin formingreactants and (b) phosphorus-containing resin forming reactantscomprising tetrakis (hydroxymethyl) phosphonium chloride and at leastone organic nitrogen compound having a molecular Weight less than 400,said nitrogen compound having at least one trivalent nitrogen atom andat least two radicals from the group consistingflof H- and -CH2OHattached to trivalent nitrogen atoms, said aqueous mixture also havingdispersed therein a powdered insoluble phosphorus-containing resin fromthe group consisting of (1) resins produced by reactingtetrakis(hydroxymethyl) phosphoniumchloride with, at least 'kenylalcohol ester of a phosphonitrilic halide with a polyhalohydrocarboncontaining at least two, halogen atoms from the group consistingoftchlorine and bromine attached to the same carbon atom, saidinsolubletpow- 12 dered. resin being. present in an amount to provide intheimixture from about 0.2 to 2.0. parts of. dispersed insoluble resinper one part of resin monomer and at least about0..1 part ofphosphorusper part of nitrogen, drying the textile, and convertingtheresin forming reactants to an insolubilized resinin situin the.textile,-the amount of impregnant being such as to provide'in the driedtex-- tile a resin addon of not more than about 35%. I

9 A process ofproducingan aqueous composition for treating textilefabrics which ,cornprisesproviding a mixture comprising an inertwater-immiscible organic liquid, an emulsifying agent, enough water toform "a stable oilin-wate r emulsion, and water-soluble resin-forming'reactants from the group messen er (a) aminoplast resin formingreactants and (b) phosphorus-containing resinfcrrning reactantscomprising tetrakis(hydroxymethyl) phosphonium chloride 'and' at leastone organic nitrogen compound having 'a molecular Weight less' than 400,said nitrogen compound having'at least one trivalent nitrogen atom andat least two radicals from the group consisting of H and CHzOH attachedto trivalent nitrogen atoms; agitating said mixture until a stableoil-in-water emulsion is formed; and then suspending in said oilin-Wateremulsion, a powdered insoluble phosphorus containing resin from thegroup consisting of (1) resins produced by reactingtetrakis(hydroxymethyl) phosphonium chloride with at least one organic'nitrogencom' pound haying at least one trivalent nitrogen atom and a atleast two radicals fromthe groupconsisting of H and CHOH attached totrivalent nitrogen atoms, (2') resins produced by' reactingtetrakis(hydroxymethyl) phosphoniurn chloride with an inorganictrivalent nitrogen-containing compound 3) resins produced byreactingtetrakis(hydroxymethyl) phosphonium chloride with a phenolic compoundcapable of condensing with formal dehyde, and (4) resins produced byreacting a terminally unsaturated polymeriz able alkenyl alcohol esterof a phosphonitrilic halide with a polyh'alohydr'oca'rbon containing atleast two halogen atoms from the" group consisting of chlorine andbromine attached to the same c'arbonatom, said insoluble powdered'resinbeing addedin an amount to provide in the resulting'compo'sition trom'about 0.2

1. A TEXTILE TREATING COMPOSITON COMPRISING AN AQUEOUS EMULSIONCONSISTING ESSENTAILLY OF AN INERT WATER-IMMISCIBLE ORGANIC LIQUID, ANDEMULSIFYING AGENT, ENOUGH WATER TO FORM A STABLE OIL-INWATER EMULSION,AND WATER-SOLUBLE RESINFORMING REACTANTS FROM THE GROUP CONSISTING OF(A) AMINOPLAST RESIN FORMING REACTANTS AND (B) PHOSPHOROUS-CONTAININGRESIN FORMING REACTANTS COMPRISING TETRAKIS(HYDROXYMETHYL) PHOSPHONIUMCHLORIDE AND AT LEAST ONE ORGANIC NITROGEN COMPOUND HAVING A MOLECULARWEIGHT LESS THAN 400, SAID NITROGEN COMPOUND HAVING AT LEAST ONETRIVALENT NITROGEN ATOM AND AT LEAST TWO RADICALS FROM THE GROUPCONSISTING OF H-AND-CH2OH ATTACHED TO TRIVALENT NITROGEN ATOMS, ANDDISPERSED IN SAID AQUEOUS EMULSION, A POWDERED INSOLUBLE PHOSPHORUS-CONTAINING RESIN FROM THE GROUP CONSISTING OF (2) RESINS PRODUCEDBY REACTING TETRAKIS(HYDROXYMETHYL) PHOSPHONIUM CHLORIDE WITH AT LEASTONE ORGANIC NITROGEN COMPOND HAVING AT LEAST ONE TRIVALENT NITROGENATOMS, AND AT LEAST TWO RADICALS FROM THE GROUP CONSISTING OFH-AND-CH2OH ATTACHED TO TRIVALENT NITROGEN ATOMS, (2) RESINS PRODUCED BYREACTING TETRAKIS(HYDROXYMETHYL) PHOSPHONIUM CHLORIDE WITH AN INORGANICTRIVALENT NITROGEN-CONTAINING COMPOUND, (3) RESINS PRODUCED BY REACTINGTETRAKIS(HYDROXYMETHYL) PHOSPHONIUM CHLORIDE WITH A PHENOLIC COMPOUNDCAPABLE OF CONDENSING WITH FORMALDEHYDE, AND (4) RESINS PRODUCED BYREACTING A TERMINALLY UNSATURATED POLYMERIZABLE ALKENYL ALCOHOL ESTER OFA PHOSPHONITRILIC HALIDE WITH A POLYHALOHYDROCARBON CONTAINING AT LEASTTWO HALOGEN ATOMS FROM THE GROUP CONSISTING OF CHLORINE AND BROMINE-.ATTACHED TO THE SAME CARBON ATOM, SAID INSOLUBLE POWDERED RESIN BEINGPRESENT IN AN AMOUNT TO PROVIDE IN THE RESULTING EMULSION-SUSPENSION,FROM ABOUT 0.2 TO 2.0 PARTS OF INSOLUBLE RESIN PER ONE PART OF RESINMONOMER, AND AT LEAST ABOUT 0.1 PART OF PHOSPHORUS PER PART OF NITROGEN.